Search Documents

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of 'cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.' Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33'7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By N. S. Stoloff, J. N. Mushovic

Age hardening response of a Mg-Th-Zr alloy has been studied at temperatures in the range 60° to 450°C. Transmission microscopy revealed clustering of thorium atoms at low aging temperatures, supporting a previous report of GP zone formation. Peak strengthening, which is observed at 325°C, is due to the formation of a coherent, ordered, DO19 type superlattice structure, of Hobable composition Mg3Th, as plates parallel to the matrix prism planes. These plates later reveal a Laves phase structure of composition Mg2Th. The equilibrium Mg4Th phase begins to precipitate in two different forms at an early stage, competitively with the Mg2Th plates. RECENT work on the Mg-Th system indicated that, unlike most magnesium-base alloys, complex precipitation phenomena may be occurring. The partial phase diagram of the Mg-Th system indicates that an equilibrium phase, Mg5Th, is the sole intermediate phase.' sturkey,' however, has reported, using X-ray and electron diffraction techniques, that a metastable fcc Laves phase, Mg2Th, precedes the formation of the equilibrium compound, which he identified as closer in composition to Mg4Th. Murakami et al.3 reported that the equilibrium phase precipitates preferentially on grain boundaries and dislocations in a Mg-1.7 wt pct Th alloy; Kent and Kelly4 aged a more dilute alloy, Mg-0.5 wt pct Th, for 4 days at 220°C and found similar results. In addition, they reported that a platelike phase with a structure close to that of the magnesium matrix forms perpendicular to the basal plane and is probably ordered. Research on a Mg-4 wt pct Th alloy by electrical resistance measurements and transmission electron microscopy has suggested that GP zones may form at low aging temperatures.3 However, the electron micrographs purporting to show this phenomenon were not conclusive. In view of the fragmentary evidence concerning the nature of the precipitation processes in the various Mg-Th alloys, an aging study was undertaken to clarify the characteristics of the various precipitates which form and to correlate the mechanical properties of the system with the direct precipitate-dislocation interactions. The latter results are presented elsewhere.' The purpose of this paper is, therefore, to discuss the precipitation sequence in this system. EXPERIMENTAL PROCEDURE Sheet stock (0.060 and 0.010 in. thick) of a commercial Mg-3.93 wt pct Th-0.42 wt pct Zr alloy (designated HK3lA) similar to that studied by sturkey2 was supplied through the courtesy of Dr. S. L. Couling of Dow Metal Products Co. Zirconium does not enter into any precipitation reactions,' but is present primarily as a grain refiner. The alloy was chill cast, warm rolled to 0.090 in. thick stock, and then finally reduced by a combination of hot and cold rolling. The alloy chemistry is given in Table I. This material was solution treated at 580°C for 4 hr in a dry CO2 atmosphere, and then water quenched. Material in this condition was fairly clear of precipitate particles and was fully recrystallized. Aging at temperatures less than 200°C was accomplished by immersing the alloy in a silicone oil bath; for higher temperatures, aging was done in a salt pot. Age hardening treatments were conducted at 60°, 80°, 105°, 135°, 160°, 250°, 325°, 350°, and 450°C for times ranging from 5 min to 400 hr. Hardness tests were performed on chemically polished 0.060-in.-thick blanks of solution treated material which were aged at the various temperatures for increasing lengths of time. For aging temperatures above 150°C the Rockwell Superficial 30T scale was employed, while samples hardened at temperatures below 150°C were monitored with the 45T scale. Each data point consists of at least three separate readings. Yield stresses also were measured at room temperature on both 0.060 and 0.010 in. sheet specimens aged at 325°C. The aged foils were thinned by the window method in a solution of 80 pct absolute alcohol and 20 pct concentrated perchloric acid (70 pct) maintained at 0°C. A stainless steel cathode was used and the applied voltage was 10 to 15 v. Thinned samples were rinsed in distilled water and pure methanol. After the me-thanol rinse the thin foils were quickly dried between filter paper. Foils prepared by the above method were examined in a Hitachi HU11B electron microscope operating at 100 kv. RESULTS A) Hardness. The hardness data are depicted in Figs. 1 and 2. Peak strengthening occurs at 325°C after aging about 6 min, see Fig. 1. Significant strengthening is achieved also at 350°C, but aging at 450°C produces only softening. The stepped curve at 250°C indicates that a complicated precipitation process may be occurring at that temperature. Fig. 2 suggests that at least two hardening mechanisms exist since the lowest temperature hardness peaks are displaced to the left of the peaks obtained at 135° and 105°C. A great deal of scatter is observed at long times in all cases due to magnesium surface degradation caused by the silicone oil bath. B) Identification of the Strengthening Precipitates. The structure formed atlowagingtemperatures (c10O°C) was not clearly resolvable by transmission microscopy. The only bright-field evidence for a change in structure was a mottled appearance which could be observed at extinction contours, as shown in Fig. 3(a), and the disappearance of this effect when dislocations produced under the influence of the electron beam passed through the matrix, as noted in

Jan 1, 1970

By R. W. Heckel

The densification of molybdenum powder by hot pressing has been studied as a function of time (up to about 3 x 104 sec) at pressures of 5000, 15,000, and 30,000 psi in the temperature range from 3700o to 1200°C. Excluding results below 2 to 5 x 10 sec, the density (D) - pressure (P) - time (t) data followed the general form:

Jan 1, 1965

By H. Bernstein

WHILE the beryllium -copper (2 pct Be) alloy is nominally nonmagnetic, the presence of iron impurity causes variations in the magnetic proper- ties which, at times, attain excessive proportions. This investigation was carried out to establish the effect of small amounts of iron on the susceptibility of the material and to determine if the effect could be minimized. Beryllium-copper is an age-hardening alloy which

Jan 1, 1959

By E. P. Whelan

A recent investigation1 into the origin of "ghost boundaries" in dilute Cd-Mg alloys has indicated the persistence of a segregated solidification substructure in spite of a homogenizing treatment designed to remove such segregation. Although no grain growth experiments have been reported on these segregated alloys, the homogenizing treatment used in grain growth studies on other dilute alloys2-7 is similar in

Jan 1, 1968

By Arnulf Muan, Klaus Schwerdtfeger

Activity-composition relations in Pt-Cr and Pd-Cr alloys of low chromium concentrations UCr < 0.3) have been determined in order to ascertain quantitatively the extent of reactions to be expected between Cr2O3-containing oxide phases and platinum or palladium crucibles used as containers in studies of oxide equilibria at low oxygen pressures. This work is a continuation of similar work previously

Jan 1, 1965

STANDING COMMITTEES. Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. . Membership. BENJAMIN B. THAYER, Chairman. KARL EILERS, JOHN H. JANEWAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman1 JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS.4 BRADLEY STOUGHTON.

Jan 10, 1913

STANDING COMMITTEES. Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership.. BENJAMIN B. THAYER, Chairman. WALTER R. INGALLS, JOHN H. JANEWAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG,Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman. JOHN HAYS HAMMOND,3 E. GIBBON SPILSBURY,2 ALEX. C. HUMPHREYS,4 BRADLEY STOUGHTON.

Jan 7, 1913

Executive SIDNEY J. JENNINGS, Chairman GEORGE D. BARRON J. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL FILERS, Chairman LEWIS W. FRANCIS J. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR L. WALKER Finance GEORGE D. BARRON, Chairman CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY,1 Chairman ALEX C. HUMPHREYS3 GEORGE C. STONE 2 J. H. JANEWAY4 BRADLEY STOUGHTON

Jan 5, 1918

STANDING COMMITTEES. Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. WALTER R. INGALLS, JOHN H. JANEWAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman. JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS,4 BRADLEY STOUGHTON.

Jan 9, 1913

Coal Transport Via Pipe Line Claimed Feasible Moving coal via pipe line is a project proposed by the U. S. Bureau of Mines. A pipe line 100 miles long capable of transporting 5000 tons of coal a day with water could be built for about $10 million. The cost of moving the coal 100 miles would be between $1.28 and $2.01 a ton.

Jan 9, 1951

Executive. CHARLES F. BAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. WALTER R. INGALLS, JOHN H. JANEWAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman 1 JOHN HAYS HAMMOND,3; E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS,4 BRADLEY STOUGHTON.

Jan 5, 1913

United Engineering Society J VIPOND DAVIES,-President WILLIAM L SAUNDERS ALFRED D FLINN Secretary GEORGE H PEGRAM, 2d Vice-president JOSEPH STRUIHERS, Treasurer HENRY A LARDNER Assistant treasurer Finance Committee House Committee WILLIAM L SAUNDERS, Chairman ALFRED D FLINN, Chairman GEORGE H PEGRAMO FREDERICK F SHARPLESS ARTHUR S DWIGHT JOHN H DUNLAP BANCROFT GHERARDI CALVIN W RICE I VIPOND DAVIES, ex-officio F L HUTCHINSON

Jan 1, 1923

STANDING COMMITTEES. . Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, , ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. KARL EILERS, JOHN H. JANEWAY, JR.., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman1 JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS 4 BRADLEY STOUGHTON.

Jan 11, 1913

STANDING COMMITTEES. Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. KARL EILERS, JOHN H. JANEWAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL .EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman 1 JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS, 4 BRADLEY STOUGHTON.

Jan 12, 1913

STANDING COMMITTEES Executive CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership BENJAMIN B. THAYER, Chairman. KARL EILERS, JOHN H. JANEWAY, Jr., JOHN D. IRVING, HERMAN A. PROSSER. Finance EDWARD L. YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library JAMES F. KEMP, Chairman.1 JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS,4 BRADLEY STOUGHTON.

Jan 1, 1914

STANDING COMMITTEES. Executive. CHARLES F. RAND, Chairman., JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. WALTER R. INGALLS, JOHN H. JANEWAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman.1 JOHN HAYS HAMMOND 3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS 4 BRADLEY STOUGHTON.

Jan 6, 1913

STANDING COMMITTEES. Executive. CHARLES F. BAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. WALTER R. INGALLS, JOHN H. JANEWAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL FILERS, JAMES GAYLEY. Library. JAM ES, F. KEMP, Chairman. JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS,4 BRADLEY STOUGHTON.

Jan 8, 1913

By William C. Sleppy

The nmgnetic susceptibility of heat-treatable aluminuin alloys is sensitive to chanyes such as solution or dissolution of solute and the precipitation of mew phases. By measuring the change in the magnetic susceptibility of aluminum alloys caused by various heat treatments, an empirical relation was found from which atomic arrangements in dilute binary alloys of copper, zinc, and magnesiutn in aluminum have been delineated. The relation predicts the ultimate formation of C1LA12 when copper is precipitated from solid solution in aluminum. Euidexce joy silovt- range order is found for copper in solid solution in aluminum in the sense that copper atoms avoid being nearest neighbors to an extent greater than would result from a purely random arrangertzeizt. Hume-Rothery has predicted such short-range order joy solid solution of copper in aluminum The Al-Zn system agrees with evidence obtained from X-ray scattering at small angles and predicts a tendency for zinc atoms to cluster in solid solution in aluminum. In the Al-mg system, the empirical relation indicates an approach to randor distribution of magnesium in solid solution in aluminum with a tendency for magnesium segvegation which increases with incveasing temperature. ThE magnetic properties of metals are complicated by the fact that contributions are made to them both by electrons of a "metallic" type which belong to the crystal as a whole, and by electrons in states localized on particular atoms. An expression1&apos;2 for the bulk magnetic susceptibility of aluminum may be written as the sum of three contributions: where XA1 is the bulk susceptibility of aluminum per gram of material (in the cgs system, the units are those of reciprocal density); Xa1+3 is the diamagnetic contribution of the electrons localized in ion cores; Xa1 is. the paramagnetic spin contribution of conduction electrons often called Pauli paramag-netism: Xa1 is the diamagnetic contribution of the conduction electrons often called Landau diamag-netism. Ion core diamagnetism arises from the precession of the electron orbits which occurs when a magnetic field is applied to a system of electrons moving about a nucleus. Its contribution to the magnetic suscepti- bility is small, temperature-independent, and unaffected by alloying. The conduction electron diamagnetism is also temperature-independent and arises from the translatory motion of the electrons. For perfectly free electrons this contribution should be exactly one-third of the Pauli spin paramagnetism, but this relation is seldom even approximately true. Blythe2 determined the conduction electron diamagnetism in pure aluminum and found it to be extremely small. Any change in the conduction electron diamagnetism caused by alloying is neglected in this work. The Pauli paramagnetic contribution3 to the magnetic susceptibility of aluminum depends upon the number of electrons that occupy excited states and whose spins can be turned parallel to an applied magnetic field. The number of electrons free to turn in the field is proportional to the temperature and each spin contribution to the susceptibility is inversely proportional to the temperature. A slight temperature dependence of Pauli paramagnetism occurs when the number of electrons occupying excited states cannot increase sufficiently to balance the inverse dependence on temperature of each spin contribution. The decrease of the magnetic susceptibility of aluminum with increasing temperature is attributed to a temperature dependence of the Pauli paramagnetism. Estimates of the Pauli paramagnetism of aluminum have been made by several workers.2,4,5 All of the values are in reasonably good agreement with each other. In this work Xal at 17°C is taken as 0.761 X 10-8 cu cm per g. An expression similar to [I] can be written for the magnetic susceptibility of an aluminum base alloy containing a fractional weight percent x of solute:&apos; Xa = (1 -x)XAl+3 +xXsoluteion * XaPauli +Xadia) [2] where X, is the magnetic susceptibility per gram of alloy, Xal&apos;3and Xsolute ion are the ion core diamag-netic contributions, and xpauli and xdia are the Pauli and diamagnetic contributions of conduction electrons in the alloy. If the components of a mixture are not alloyed but simply mixed together in their pure states without producing a new phase, then the magnetic susceptibility of the mixture is given by the Wiedemann additivity law: Xm =x1X1 +x2x2 + ..xnxp [3] where X, is the susceptibility per gram of mixture and xnXp are the weight fractions and susceptibilities, respectively,-. for the pure components. The additivity law is not applicable to alloys because the outer electronic structures of the components are changed by alloying.&apos; Both the Pauli paramagnetism and Landau diamagnetism are affected; hence the magnetic susceptibilitv of an alloy is usually different from that calculated using the additivity law. In this work the difference, X, -X,, is taken as a measure of the change caused by alloying.

Jan 1, 1968

By T. L. MacKay

Oxidation rates of single-crystal and poly crystalline zirconium in oxygen at temperatures from 307° to 815°C obey the parabolic rate law for short ex-posure time, 4 to 6 hr. The activation energy for the oxidation of single-crystal zirconium between 420° and 790°C is 42.6 ± 0.7 kcal per mole, and in the temperature range 307" to 600°C the activation energy for oxidation of poly crystalline zirconium is approximately the same. The high-activation energy is indicative that diffusion through the bulk oxide film is the primary mode of mass transport for both types of metal. The higher oxidation rates for poly -crystalline zirconium in this temperature range were attributed to differences in the orientation of the grains in the metal with respect to the oxidizing surfaces. Above 600°C, vain growth was observed in polycrystalline zirconium, and the oxidation rates approached those of single-crystal zirconium. ThE kinetic data of previous oxidation studies1-&apos; of zirconium in oxygen have been interpreted by both parabolic and cubic rate laws. There is some evidence that there is a transition from the parabolic to the cubic rate law at prolonged exposures, but the question is still controversial. For the parabolic rate law activation energies are reported in the range 18.6 to 35 kcal per mole, and for the cubic rate law in the range 38 to 47 kcal per mole. So far as the mechanism of zirconium oxidation is concerned, inert marker studies10,11 have indicated that the oxidation proceeds by oxygen (anion) diffusion through the oxide film toward the metal-metal oxide interface. Pemslerl2 observed that the orientation of the grains in the zirconium metal substrate affected the rate of formation of the oxide film on the surfaces of the grains and that the orientation dependence of the corrosion rate persisted beyond the initial stages of reaction. The rate of oxidation was a minimum when the c axis of the grain was parallel to the surface of the sample, and rose to a maximum when the c axis was inclined at about 20 deg to the plane of sample surface, and decreased again at higher inclinations. cox13 observed that in 300°C steam a thin oxide film was formed initially on zirconium and that this oxide film, which exhibited interference colors, became dark first along the grain boundaries and then over the whole surface in an inhomogeneous manner as the film thickened. Cox proposed a mechanism in which oxygen diffused along preferred paths created by grain boundaries in the metal and formed a much thicker film at or near the grain boundary than on the central zone of the grain. In the present study, the oxidation rates of single crystals of zirconium were measured in oxygen and compared with the oxidation rates of polycrystalline zirconium of the same bar stock. It was felt that such a comparison would elucidate the role of grain boundaries in the metal substrate. SAMPLE PREPARATION Single crystals of zirconium were prepared by following the procedure of I3apperport,14 starting with 1/4-in. rod purchased as crystal-bar zirconium. Zirconium rods 2 in. long were wrapped in tungsten foil and sealed in quartz tubes at pressures of less than 10-6 mm of mercury. Large single crystals were grown by thermal cycling above and below the a-/3 transformation temperature, 862°C. Several specimens were simultaneously subjected to the same cycling procedure, heating to 1200°C, holding for 4 hr, then cooling in the furnace and holding at a temperature of 840°C for 5 to 10 days. This cycle was repeated five or six times for each set of specimens. The grain size of the crystal-bar zirconium before thermal cycling was between 10 and 30 p. Fig. 1 shows the microstructure of an end section of as-received crystal-bar zirconium. A longitudinal section of each zirconium rod after thermal cycling was polished and examined under polarized light, see Fig. 2, and the largest single crystals were selected for this study. Zirconium rods 1/8 in. in diameter and 1/2 in. long with spherical ends were machined from the single crystals and from the as-received bar stock. An X-ray examination showed that the c axis of the single crystals made either a 34-deg or an 89-deg angle with the rod axis. The specimens were chemically etched for 2 min in solution consisting of 15 parts hydrofluoric acid (48 pct), 80 parts nitric acid, and 80 parts water. The chemical polish removed 1 to 2 mils from the surface. EXPERIMENTAL The Sartorius vacuum microbalance used in this study has a sensitivity of 0.5 pg and a capacity of

Jan 1, 1963